Acrylonitrile derivatives as additive for electrolytes in lithium ion batteries

ABSTRACT

An electrolyte composition (A) containing (i) at least one aprotic organic solvent; (ii) at least one conducting salt; (iii) at least one compound of formula (I) wherein X 1  and X 2  are independently from each other selected from N(R 1 ), P(R 1 ), O, and S, Y 1  and Y 2  are independently from each other selected from (O), (S), (PR 2 ) and (NR 2 ); and electrochemical cells containing electrolyte composition (A).

The present invention relates to an electrolyte composition (A)containing

(i) at least one aprotic organic solvent;

(ii) at least one conducting salt;

(iii) at least one compound of formula (I)

-   -   wherein    -   X¹, X², Y¹, and Y² are defined below, and

(iv) optionally at least one further additive.

The present invention further relates to the use of compounds of formula(I) as additives for electrolytes in electrochemical cells and toelectrochemical cells comprising the above described electrolytecomposition (A), at least one cathode (B) comprising at least onecathode active material, and at least one anode (C) comprising at leastone anode active material.

Storing electrical energy is a subject of still growing interest.Efficient storage of electric energy would allow electric energy to begenerated when it is advantageous and used when needed.

Accumulators, for example lead accumulators and nickel-cadmiumaccumulators, have been known for many decades. The known leadaccumulators and nickel-cadmium accumulators have the disadvantages,however, of a comparatively low energy density and of a memory effectwhich reduces the rechargeability and hence the useful life of leadaccumulators and nickel-cadmium accumulators.

Lithium ion accumulators, frequently also referred to as lithium ionbatteries, are used as an alternative. They provide higher energydensities than accumulators based on lead or comparatively noble heavymetals.

Since many lithium ion batteries utilize metallic lithium or lithium inoxidation state 0, or produce it as an intermediate, they are watersensitive. Moreover, the conductive salts used, for example LiFP₆, arewater sensitive during long-term operation. Water is therefore not ausable solvent for the lithium salts used in lithium ion batteries.Instead, organic carbonates, ethers, esters and ionic liquids are usedas sufficiently polar solvents. Most state of the art lithium ionbatteries in general comprise not a single solvent but a solvent mixtureof different organic aprotic solvents. During charge and discharge oflithium ion batteries various reactions take place at different cellpotentials. It is known that during the first charging process of alithium ion battery usually a film is formed on the anode. This film isoften called solid electrolyte interface (SEI). The SEI is permeable forlithium ions and protects the electrolyte from direct contact with theanode and vice versa. It is formed by reductive decomposition ofcomponents of the electrolyte composition like solvents, e.g.carbonates, esters, and ethers, and conductive salts on the surface ofthe anode, especially if the anode active material is a carbonaceousmaterial like graphite. A certain amount of the lithium from the cathodeis irreversibly consumed for the formation of the SEI and cannot bereplaced. One possibility to reduce the amount of irreversibly consumedlithium is the addition of suitable chemical compounds which are easilydecomposed on the anode by reduction and thereby forming a film on thesurface of the anode. One especially well suited compound is vinylenecarbonate, see for instance EP 0 683 587 B1 and U.S. Pat. No. 6,413,678B1. Vinylene carbonate forms a stable SEI on a graphite anode in lithiumion batteries.

Other film forming additives are known, inter alia acrylonitrile andderivatives thereof. Santner et al., J. Power Sources, 2003, 119 to 121,pages 368 to 372 reports the use of acrylonitrile in propylene carbonateas film forming additive in lithium ion secondary batteries having agraphite anode and LiMn₂O₄ as cathode active material. US2006/0194118 A1discloses electrolyte composition for lithium ion batteries containingat least one first additive capable o forming a chelating complex with atransition metal and being stale at voltages ranging from about 2.5 to4.8 V. Said first additive may be inter alia 1,2-dicyanoethylene or1,2-dicyanobenzene. JP 2012195223 A2 discloses the use of substitutedbenzonitrile derivatives in electrolytes for lithium ion batteries. FromEP 2 120 279 A1 electrolytic solutions for secondary batteriescontaining acrylonitrile derivatives like methacrylonitrile,2-furonitrile, fumaronitrile and tetracyanoethylene are known. U.S. Pat.No. 7,008,728 B2 describes electrolytes for lithium secondary batteriescontaining acrylonitrile or derivatives thereof as additives forming anorganic SEI on the negative electrode during initial charging. US2004/0013946 A1 is directed to non-aqueous electrolytic solutions forlithium batteries containing at least one nitrile compound likeactetonitrile or 1,2-dicyanobenzene and at least on S═O group containingcompound. WO 2012/029386 A1 discloses lithium ion batteries containingacrylonitrile compounds in the electrolyte composition, e.g.2-furonitrile. From US 2011/207000A1 the use of benzonitrilederivatives, in particular of fluorinated benzonitriles as additives inelectrolytes for electrochemical cells is known. JP 2003-086248 Aconcerns electrolytic solutions for secondary batteries containingcompounds having an electrophilic group conjugated with a carbon-carbonunsaturated bond. These compounds may inter alia be selected fromacrylonitrile, methacrylonitrile and 2-cyanoacrylic acid ethyl ester.

Nevertheless there is still the need for enhancing the lifetime ofsecondary batteries and a demand for electrolyte additives leading to aprolonged life time and cycle stability of secondary lithium ionbatteries.

It was an object of the present invention to provide an electrolytecomposition leading to an improved lifetime of lithium ion batteries. Afurther object of the present invention was to provide lithium ionbatteries of high energy density and/or higher operating voltage havinggood performance characteristics and long lifetime.

This object is achieved by an electrolyte composition (A) containing

(i) at least one aprotic organic solvent;

(ii) at least one conducting salt;

(iii) at least one compound of formula (I)

-   -   wherein    -   X¹ and X² are independently from each other selected from N(R¹),        P(R¹), O, and S;    -   R¹ is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,        C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and        C(O)OR³, wherein alkyl, (hetero)cycloalkyl, alkenyl,        (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may be        substituted by one or more substituents selected from F, CN,        C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇        (hetero)aryl, S(O)₂OR^(3a), OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a),        C(O)R^(3a), C(O)OR^(3a), NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);        -   Y¹ and Y² are independently from each other selected from            (O), (S), (PR²) and (NR²),    -   R² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,        C₂-C₁₀ alkenyl, (hetero)C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) and C(O)R^(2a), wherein        alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,        alkynyl, (hetero)aryl, and aralkyl may be substituted by one or        more substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,        S(O)₂OR^(2b), OS(O)₂R^(2b), S(O)₂R^(2b), OR^(2b), C(O)R^(2b),        C(O)OR^(10b), NR^(2b)R^(2c), and NC(O)R^(2b)R^(2c); and    -   R^(2a), R^(2b) and R^(2c) are independently from each other        selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀        alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl,        (hetero)cycloalkyl, alkenyl, and (hetero)aryl may be substituted        by one or more substituents selected from F and CN,    -   R³, R⁴, R^(3a), and R^(3b) are selected independently from each        other from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀        alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇        (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl,        (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,        (hetero)aryl, and aralkyl may be substituted by one or more        substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆        (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,        S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c), OR^(3c), C(O)R^(3c),        C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);    -   R^(3c) and R^(3d) are selected independently from each other        from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl,        and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,        alkenyl, and (hetero)aryl may be substituted by one or more        substituents selected from F and CN;

and (iv) optionally, at least one further additive.

The problem is further solved by the use of at least one compound offormula (I) as additive for electrolytes in electrochemical cells; andby the electrochemical cell comprising the electrolyte composition (A)as described above, at least one cathode (B) comprising at least onecathode active material, and at least one anode (C) comprising at leastone anode active material.

The addition of at least one compound of general formula (I) to anelectrolyte for lithium ion secondary batteries comprising at least oneaprotic organic solvent or a mixture thereof and at least one conductingsalt leads to improved capacity retention of the lithium secondary ionbatteries.

The inventive electrolyte composition (A) is preferably liquid atworking conditions; more preferred it is liquid at 1 bar and 25° C.,even more preferred the electrolyte composition is liquid at 1 bar and−15° C., in particular the electrolyte composition is liquid at 1 barand −30° C., even more preferred the electrolyte composition is liquidat 1 bar and −50° C.

The electrolyte composition (A) contains at least one aprotic organicsolvent (i), preferably at least two aprotic organic solvents (i).According to one embodiment the electrolyte composition (A) may containup to ten aprotic organic solvents (i).

The at least one aprotic organic solvent (i) is preferably selected from

(a) cyclic and noncyclic organic carbonates, which may be partlyhalogenated,

(b) di-C₁-C₁₀-alkylethers, which may be partly halogenated,

(c) di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers and polyethers, which may bepartly halogenated,

(d) cyclic ethers, which may be partly halogenated,

(e) cyclic and acyclic acetales and ketales, which may be partlyhalogenated,

(f) orthocarboxylic acids esters, which may be partly halogenated,

(g) cyclic and noncyclic esters of carboxylic acids, which may be partlyhalogenated,

(h) cyclic and noncyclic sulfones, which may be partly halogenated,

(i) cyclic and noncyclic nitriles and dinitriles, which may be partlyhalogenated, and

(j) ionic liquids, which may be partly halogenated.

More preferred the at least one aprotic organic solvent (i) is selectedfrom cyclic and noncyclic organic carbonates (a), di-C₁-C₁₀-alkylethers(b), di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers and polyethers (c) and cyclicund acyclic acetales and ketales (e), even more preferred electrolytecomposition (A) contains at least one aprotic organic solvent (i)selected from cyclic and noncyclic organic carbonates (a) and mostpreferred electrolyte composition (A) contains at least two aproticorganic solvents (i) selected from cyclic and noncyclic organiccarbonates (a), in particular preferred electrolyte composition (A)contains at least one aprotic solvent (i) selected from cyclic organiccarbonates and at least one aprotic organic solvent (i) selected fromnoncyclic organic carbonates.

The aprotic organic solvents (a) to (j) may be partly halogenated, e.g.they may be partly fluorinated, partly chlorinated or partly brominated,preferably they may be partly fluorinated. “Partly halogenated” means,that one or more H of the respective molecule is substituted by ahalogen atom, e.g. by F, Cl or Br. Preference is given to thesubstitution by F. The at least one solvent (i) may be selected frompartly halogenated and non-halogenated aprotic organic solvents (a) to(j), i.e. the electrolyte composition may contain a mixture of partlyhalogenated and non-halogenated aprotic organic solvents.

Examples of suitable organic carbonates (a) are cyclic organiccarbonates according to the general formula (a1), (a2) or (a3)

wherein

R^(a), R^(b) und R^(c) being different or equal and being independentlyfrom each other selected from hydrogen; C₁-C₄-alkyl, preferably methyl;F; and C₁-C₄-alkyl substituted by one or more F, e.g. CF₃.

“C₁-C₄-alkyl” is intended to include methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec.-butyl and tert.-butyl.

Preferred cyclic organic carbonates (a) are of general formula (a1),(a2) or (a3) wherein R^(a), R^(b) and R^(c) are H. Examples are ethylenecarbonate, vinylene carbonate, and propylene carbonate. A preferredcyclic organic carbonate (a) is ethylene carbonate. Further preferredcyclic organic carbonates (a) are difluoroethylene carbonate (a4) andmonofluoroethylene carbonate (a5)

Examples of suitable non-cyclic organic carbonates (a) are dimethylcarbonate, diethyl carbonate, methylethyl carbonate and mixturesthereof.

In one embodiment of the invention the electrolyte composition (A)contains mixtures of noncyclic oganic carbonates (a) and cyclic organiccarbonates (a) at a ratio by weight of from 1:10 to 10:1, preferred offrom 3:1 to 1:3.

Examples of suitable non-cyclic di-C₁-C₁₀-alkylethers (b) aredimethylether, ethylmethylether, diethylether, diisopropylether, anddi-n-butylether.

Examples of di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers (c) are1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme (diethylene glycoldimethyl ether), triglyme (triethylenglycol dimethyl ether), tetraglyme(tetraethylenglycol dimethyl ether), and diethylenglycoldiethylether.

Examples of suitable polyethers (c) are polyalkylene glycols, preferablypoly-C₁-C₄-alkylene glycols and especially polyethylene glycols.Polyethylene glycols may comprise up to 20 mol % of one or moreC₁-C₄-alkylene glycols in copolymerized form. Polyalkylene glycols arepreferably dimethyl- or diethyl-end capped polyalkylene glycols. Themolecular weight M_(w) of suitable polyalkylene glycols and especiallyof suitable polyethylene glycols may be at least 400 g/mol. Themolecular weight M_(w) of suitable polyalkylene glycols and especiallyof suitable polyethylene glycols may be up to 5 000 000 g/mol,preferably up to 2 000 000 g/mol.

Examples of suitable cyclic ethers (d) are tetrahydrofurane and1,4-dioxane.

Examples of suitable non-cyclic acetals (e) are 1,1-dimethoxymethane and1,1-diethoxymethane. Examples for suitable cyclic acetals (e) are1,3-dioxane and 1,3-dioxolane.

Examples of suitable orthocarboxylic acids esters (f) are tri-C₁-C₄alkoxy methane, in particular trimethoxymethane and triethoxymethane.

Examples of suitable noncyclic esters of carboxylic acids (g) are ethylacetate, methyl butanoate, and esters of dicarboxylic acids like1,3-dimethyl propanedioate. An example of a suitable cyclic ester ofcarboxylic acids (lactones) is γ-butyrolactone.

Examples of suitable cyclic and noncyclic sulfones (h) are ethyl methylsulfone and tetrahydrothiophene-1,1-dioxide.

Examples of suitable cyclic and noncyclic nitriles and dinitriles (i)are adiponitrile, acetonitrile, propionitrile, butyronitrile.

The water content of the inventive electrolyte composition is preferablybelow 100 ppm, based on the weight of the electrolyte composition, morepreferred below 50 ppm, most preferred below 30 ppm. The water contentmay be determined by titration according to Karl Fischer, e.g. describedin detail in DIN 51777 or ISO760: 1978.

The content of HF of the inventive electrolyte composition is preferablybelow 60 ppm, based on the weight of the electrolyte composition, morepreferred below 40 ppm, most preferred below 20 ppm. The HF content maybe determined by titration according to potentiometric orpotentiographic titration method.

The inventive electrolyte composition (A) furthermore contains at leastone conducting salt (ii). Electrolyte composition (A) functions as amedium that transfers ions participating in the electrochemical reactiontaking place in an electrochemical cell. The conducting salt(s) (ii)present in the electrolyte are usually solvated in the aprotic organicsolvent(s) (i). Preferably the conducting salt (ii) is a lithium salt.The conducting salt is preferably selected from the group consisting of

-   -   Li[F_(6−x)P(C_(y)F_(2y+1))_(x)], wherein x is an integer in the        range from 0 to 6 and y is an integer in the range from 1 to 20;        -   Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O)] and Li[B(OR^(II)O)₂]            wherein each R^(I) is independently from each other selected            from F, Cl, Br, I, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄            alkynyl, wherein alkyl, alkenyl, and alkynyl may be            substituted by one or more OR^(III), wherein R^(III) is            selected from C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl,            and        -   (OR^(II)O) is a bivalent group derived from a 1,2- or            1,3-diol, a 1,2- or 1,3-dicarboxlic acid or a 1,2- or            1,3-hydroxycarboxylic acid, wherein the bivalent group forms            a 5- or 6-membered cycle via the both oxygen atoms with the            central B-atom;    -   LiClO₄; LiAsF₆; LiCF₃SO₃; Li₂SiF₆; LiSbF₆; LiAlCl₄, lithium        tetrafluoro (oxalato) phosphate; lithium oxalate; and    -   salts of the general formula Li[Z(C_(n)F_(2n+1)SO₂)_(m)], where        m and n are defined as follows:        -   m=1 when Z is selected from oxygen and sulfur,        -   m=2 when Z is selected from nitrogen and phosphorus,        -   m=3 when Z is selected from carbon and silicon, and        -   n is an integer in the range from 1 to 20.

Suited 1,2- and 1,3-diols from which the bivalent group (OR^(II)O) isderived may be aliphatic or aromatic and may be selected, e.g., from1,2-dihydroxybenzene, propane-1,2-diol, butane-1,2-diol,propane-1,3-diol, butan-1,3-diol, cyclohexyl-trans-1,2-diol andnaphthalene-2,3-diol which are optionally are substituted by one or moreF and/or by at least one straight or branched non fluorinated, partlyfluorinated or fully fluorinated C₁-C₄ alkyl group. An example for such1,2- or 1,3-diole is 1,1,2,2-tetra(trifluoromethyl)-1,2-ethane diol.

“Fully fluorinated C₁-C₄ alkyl group” means, that all H-atoms of thealkyl group are substituted by F.

Suited 1,2- or 1,3-dicarboxlic acids from which the bivalent group(OR^(II)O) is derived may be aliphatic or aromatic, for example oxalicacid, malonic acid (propane-1,3-dicarboxylic acid), phthalic acid orisophthalic acid, preferred is oxalic acid. The 1,2- or 1,3-dicarboxlicacid are optionally substituted by one or more F and/or by at least onestraight or branched non fluorinated, partly fluorinated or fullyfluorinated C₁-C₄ alkyl group.

Suited 1,2- or 1,3-hydroxycarboxylic acids from which the bivalent group(OR^(II)O) is derived may be aliphatic or aromatic, for examplesalicylic acid, tetrahydro salicylic acid, malic acid, and 2-hydroxyacetic acid, which are optionally substituted by one or more F and/or byat least one straight or branched non fluorinated, partly fluorinated orfully fluorinated C₁-C₄ alkyl group. An example for such 1,2- or1,3-hydroxycarboxylic acids is 2,2-bis(trifluoromethyl)-2-hydroxy-aceticacid.

Examples of Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O)] and Li[B(OR^(II)O)₂]are LiBF₄, lithium difluoro oxalato borate and lithium dioxalato borate.

Preferably the at least one conducting salt (ii) is selected fromLiAsF₆, Li[N(FSO₂)₂], Li[N(CF₃SO₂)₂], LiClO₄, LiPF₆, LiBF₄, andLiPF₃(CF₂CF₃)₃, more preferred the conducting salt (ii) is selected fromLiPF₆ and LiBF₄, and the most preferred conducting salt (ii) is LiPF₆.

The at least one conducting salt (ii) is usually present at a minimumconcentration of at least 0.01 wt.-%, preferably of at least 1 wt.-%,and more preferred of at least 5 wt.-%, based on the total weight of theelectrolyte composition. Usually the upper concentration limit for theat least one conducting salt (ii) is 25 wt.-%, based on the total weightof the electrolyte composition.

The inventive electrolyte composition (A) contains as component (iii) atleast one compound of formula (I)

wherein

-   X¹ and X² are independently from each other selected from N(R¹),    P(R¹), O, and S; preferably X¹ and X² are independently from each    other selected from N(R¹) and O;-   R¹ is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,    C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and C(O)OR³,    wherein alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,    alkynyl, (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),    OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), C(O)OR^(3a),    NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b);-   Y¹ and Y² are independently from each other selected from (O), (S),    (PR²) and (NR²),-   R² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,    C₂-C₁₀ alkenyl, (hetero)C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) and C(O)R^(2a), wherein alkyl,    (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,    (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(2b),    OS(O)₂R^(2b), S(O)₂R^(2b), OR^(2b), C(O)R^(2b), C(O)OR^(10b),    NR^(2b)R^(2c), and NC(O)R^(2b)R^(2c); and-   R^(2a), R^(2b) and R^(2c) are independently from each other selected    from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and    C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN,-   R³, R⁴, R^(3a), and R^(3b) are selected independently from each    other from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀    alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl,    alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl    may be substituted by one or more substituents selected from F, CN,    C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇    (hetero)aryl, S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c), OR^(3c),    C(O)R^(3c), C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d); and-   R^(3c) and R^(3d) are selected independently from each other from H,    C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and C₅-C₇    (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN.

The term “C₁-C₁₀ alkyl” as used herein means a straight or branchedsaturated hydrocarbon group with 1 to 10 carbon atoms having one freevalence. Preferred examples of C₁-C₁₀ alkyl are C₁-C₆ alkyl and include,e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl,iso-hexyl, 2-ethyl hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl,n-nonyl, n-decyl and the like. Preferred are C₁-C₄ alkyl groups and mostpreferred are 2-propyl, methyl and ethyl. C₁-C₁₀ alkyl may besubstituted by one or more groups or atoms selected from CN, F, OR^(3a),and/or one or more non-adjacent C-atoms of C₁-C₁₀ alkyl may be replacedby oxygen or sulfur. Preferably, in C₁-C₁₀ alkyl no C atoms are replacedby oxygen or sulfur.

The term “C₃-C₆ (hetero)cycloalkyl” as used herein means a cyclicsaturated hydrocarbon group with 3 to 6 carbon atoms having one freevalence wherein one or more C-atoms may be replaced by N, O or S.Examples of C₃-C₆ cycloalkyl include cyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl, preferred is cyclohexyl. Examples of C₃-C₆hetero cycloalkyl are oxiranyl and tetrahydrofuryl, preferred isoxiranyl.

The term “C₂-C₁₀ alkenyl” as used herein refers to an unsaturatedstraight or branched hydrocarbon group with 2 to 10 carbon atoms havingone free valence. Unsaturated means that the alkenyl group contains atleast one C—C double bond. Preferred examples of C₂-C₁₀ alkenyl areC₂-C₆ alkenyl including for example ethenyl (vinyl), 1-propenyl,2-propenyl, 1-n-butenyl, 2-n-butenyl, iso-butenyl, 1-pentenyl, 1-hexenyland the like. Preferred are C₂-C₄ alkenyl groups and in particularethenyl and propenyl, the preferred propenyl is 1-propen-3-yl, alsocalled allyl.

The term “C₃-C₆ (hetero)cycloalkenyl” as used herein refers to a cyclicunsaturated hydrocarbon group with 3 to 6 carbon atoms having one freevalence wherein one or more C-atoms may be replaced by N, O or S.Unsaturated means that the cycloalkenyl contains at least one C—C doublebond. Examples of C₃-C₆ (hetero)cycloalkenyl are cyclopropen,cycolbuten, cyclopenten, and cyclohexen.

The term “C₂-C₆ alkynyl” as used herein refers to an unsaturatedstraight or branched hydrocarbon group with 2 to 6 carbon atoms havingone free valence, wherein the hydrocarbon group contains at least oneC—C triple bond. C₂-C₁₀ alkynyl includes for example ethynyl,1-propynyl, 2-propynyl, 1-n-butinyl, 2-n-butynyl, iso-butinyl,1-pentynyl, 1-hexynyl and the like. Preferred is C₂-C₄ alkynyl, inparticular propynyl. The preferred propenyl is 1-propyn-3-yl also calledpropargyl.

The term “C₅-C₇ (hetero)aryl” as used herein denotes an aromatic 5- to7-membered hydrocarbon cycle having one free valence, wherein one ormore C-atom may be replaced by N, O or S. An example of C₅-C₇ aryl isphenyl, examples of C₅-C₇ heteroaryl are pyrrolyl, furanyl, thiophenyl,pyridinyl, pyranyl, and thiopyranyl.

The term “C₇-C₁₃ aralkyl” as used herein denotes an aromatic 5- to7-membered hydrocarbon cycle substituted by one or more C₁-C₆ alkyl. TheC₇-C₁₃ aralkyl group contains in total 7 to 13 C-atoms and has one freevalence. The free valence may be located in the aromatic cycle or in aC₁-C₆ alkyl group, i.e. C₇-C₁₃ aralkyl group may be bound via thearomatic part or via the alkyl part of the group. Examples of C₇-C₁₃aralkyl are methylphenyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl,1,4-dimethylphenyl, ethylphenyl, 2-propylphenyl, and the like.

According to one embodiment of the present invention the at least onecompound of formula (I) is selected from compounds of formula (I)

wherein

-   X¹ and X² are independently from each other selected from N(R¹);-   R¹ is selected from H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₅-C₇    (hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, alkenyl    (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, OR^(3a), C(O)R^(3a),    C(O)OR^(3a), S(O)₂OR^(3a), and OS(O)₂R^(3a);-   R² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,    C₂-C₁₀ alkenyl, (hetero)C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) and C(O)R^(2a), wherein alkyl,    (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,    (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(2b),    OS(O)₂R^(2b), S(O)₂R^(2b), OR^(2b), C(O)R^(2b), C(O)OR^(10b),    NR^(2b)R^(2c), and NC(O)R^(2b)R^(2c); and-   R^(2a), R^(2b) and R^(2c) are independently from each other selected    from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and    C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN,

R³, R⁴, and R^(3a) is selected from H, C₁-C₆ alkyl, and C₂-C₆ alkenyl,wherein alkyl and alkenyl may be substituted by one or more substituentsselected from F and CN;

According to another embodiment of the present invention the at leastone compound of formula (I) is selected from compounds of formula (I)wherein both Y¹ and Y² are the same and each selected from (O) and NR¹.

According to another preferred embodiment of the present inventionwherein the at least one compound of formula (I) is selected fromcompounds of formula (I a) wherein

wherein

-   X¹ and X² are selected independently from each other from N(R¹),    P(R¹), O, and S, preferably X¹ and X² are selected independently    from each other from N(R¹) and O, and-   A¹ and A² are combined and form together with X¹ and X² and the C—C    double bond a 6-membered unsaturated heterocycle-   Y¹ and Y² are independently from each other are selected from (O),    (S), (PR²) and (NR²), and-   R² is selected from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,    C₂-C₁₀ alkenyl, (hetero)C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇    (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) and C(O)R^(2a), wherein alkyl,    (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,    (hetero)aryl, and aralkyl may be substituted by one or more    substituents selected from F, CN, C₁-C₆ alkyl, C₃-C₆    (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(2b),    OS(O)₂R^(2b), S(O)₂R^(2b), OR^(2b), C(O)R^(2b), C(O)OR^(2b),    NR^(2b)R^(2c), and NC(O)R^(2b)R^(2c); and-   R^(2a), R^(2b) and R^(2c) are independently from each other selected    from H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, and    C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and    (hetero)aryl may be substituted by one or more substituents selected    from F and CN.

Preferred compounds of formula (I a) are compounds

wherein

-   X¹ and X² are independently from each other N(R¹); and-   Y¹ and Y² are (O).

More preferred compounds of formula (Ia) are compounds

wherein

-   X¹ and X² are independently from each other N(R¹);-   each R¹ is independently from each other selected from H, C₁-C₆    alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl, wherein alkyl, alkenyl, and    alkynyl may be substituted by one or more substituents selected from    F, CN, OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), and    C(O)OR^(3a);-   R^(3a) is selected from C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₂-C₆    alkynyl, wherein alkyl, alkenyl, and alkynyl may be substituted by    one or more substituents selected from F, CN, and OR^(3c);-   R^(3c) is selected from H, and C₁-C₆ alkyl which may be substituted    by one or more substituents selected from F and CN; and-   Y¹ and Y² are (O).

Particularly preferred example of compounds of formula (I a) is compound(1.1):

The electrolyte composition (A) may contain at least one furtheradditive (iv) which is selected from the group consisting of vinylenecarbonate and its derivatives, vinyl ethylene carbonate and itsderivatives, methyl ethylene carbonate and its derivatives, lithium(bisoxalato) borate, lithium difluoro (oxalato) borate, lithiumtetrafluoro (oxalato) phosphate, lithium oxalate, 2-vinyl pyridine,4-vinyl pyridine, cyclic exo-methylene carbonates, sultones, cyclic andacyclic sulfonates, cyclic and acyclic sulfites, cyclic and acyclicsulfinates, organic esters of inorganic acids, acyclic and cyclicalkanes having a boiling point at 1 bar of at least 36° C., and aromaticcompounds, optionally halogenated cyclic and acyclic sulfonylimides,optionally halogenated cyclic and acyclic phosphate esters, optionallyhalogenated cyclic and acyclic phosphines, optionally halogenated cyclicand acyclic phosphites including, optionally halogenated cyclic andacyclic phosphazenes, optionally halogenated cyclic and acyclicsilylamines, optionally halogenated cyclic and acyclic halogenatedesters, optionally halogenated cyclic and acyclic amides, optionallyhalogenated cyclic and acyclic anhydrides, ionic liquids, and optionallyhalogenated organic heterocycles. The additive (iv) is preferablyselected to be different from the compound selected as conducting salt(ii) present in the respective electrolyte composition (A). Preferablyadditive (iv) is also different from the at least one organic aproticsolvent (i) present in the respective electrolyte composition (A).

Preferred ionic liquids according to the present invention are selectedfrom ionic liquids of formula [K][L] in which:

[K] denotes a cation, preferably reduction-stable, selected from thecation groups of the general formulae (II) to (IX)

wherein

-   R denotes H, C₁- to C₅-alkyl, C₂- to C₆-alkenyl, and phenyl,    preferably methyl, ethyl, and propyl;-   R^(A) denotes —(CH₂)_(s)—O—C(O)—R, —(CH₂)_(s)—C(O)—OR,    —(CH₂)_(s)—S(O)₂—OR, —(CH₂)_(s)—O—S(O)₂—R, —(CH₂)_(s)—O—S(O)₂—OR,    —(CH₂)_(s)—O—C(O)—OR, —(CH₂)_(s)—HC═CH—R, —(CH₂)_(s)—CN,

-   -   wherein individual CH₂ groups may be replaced by O, S or NR and        s=1 to 8, preferably s =1 to 3;

-   X^(A) denotes CH₂, O, S or NR^(B);

-   R^(B) denotes H, C₁- to C₆-alkyl, C₂- to C₆-alkenyl, phenyl, and    —(CH₂)_(s)—CN with s=1 to 8, preferably s=1 to 3; preferably R^(B)    is methyl, ethyl, propyl or H; and

-   [L] denotes an anion selected from the group BF₄ ⁻, PF₆,    [B(C₂O₄)₂]⁻, [F₂B(C₂O₄)], [N(S(O)₂F)₂]⁻,    [F_(p)P(C_(q)F_(2q+1))_(6−p)]⁻, [N(S(O)₂C_(q)F_(2q+1))₂]⁻,    [(C_(q)F_(2q+1))₂P(O)O]⁻, [C_(q)F_(2q+1)P(O)O₂]²⁻,    [OC(O)C_(q)F_(2q+1]) ⁻, [OS(O)₂C_(q)F_(2q+1)]⁻;    [N(C(O)C_(q)F_(2q+1))₂]⁻;    [N(C(O)C_(q)F_(2q+1))(S(O)₂C_(q)F_(2q+1))]⁻;    [N(C(O)C_(q)F_(2q+1))(C(O))F]⁻;

-   [N(S(O)₂C_(q)F_(2q+1))(S(O)₂F)]⁻; [C(C(O)C_(q)F_(2q+1))₃]⁻, and    [C(S(O)₂C_(q)F_(2q+1))₃N(SO₂CF₃)₂]⁻,

wherein p is an integer in the range from 0 to 6 and q is an integer inthe range from 1 to 20, preferably q is an integer in the ranger from 1to 4.

Preferred ionic liquids for use as additive (iv) are ionic liquids offormula [K][L] in which [K] is selected from pyrrolidinium cations offormula (II) with X is CH₂ and s is an integer in the range of from 1 to3 and [L] is selected from the group consisting of BF₄ ⁻, PF₆,[B(C₂O₄)₂]⁻, [F₂B(C₂O₄)]⁻, [N(S(O)₂F)₂]⁻, [N(SO₂C₂F₅)₂ ²],[F₃P(C₂F₅)₃]⁻, and [F₃P(C₄F₉)₃]⁻.

If one or more further additives (iv) are present in the electrolytecomposition (A), the total concentration of further additives (iv) is atleast 0.001 wt.-%, preferred 0.005 to 5 wt.-% and most preferred 0.01 to2 wt.-%, based on the total weight of the electrolyte composition (A).

A further object of the present invention is the use of at least onecompound of formula (I) as defined above as additive for electrolytes inelectrochemical cells, preferably in lithium ion secondaryelectrochemical cells.

The compounds of general formula (I) are well-suited as film formingadditives in electrochemical cells. The film may be formed on the anodeand/or on the cathode. Preferably the compounds of general formula (I)are used as film forming additives in lithium ion secondaryelectrochemical cells, in particular as additives forming a film on thecathode of lithium ion secondary electrochemical cells.

The compounds of general formula (I) are usually added to theelectrolyte composition to yield a concentration of from is 0.001 to 10wt.-%, preferred 0.01 to 2 wt.-%, more preferred 0.01 to <1 wt.-%, mostpreferred 0.01 to 0.9 wt.-%, and in particular 0.01 to 0.75 wt.-%, basedon the total weight of the electrolyte composition (A).

Another object of the present invention is an electrochemical cellcomprising

-   (A) the electrolyte composition as described above,-   (B) at least one cathode comprising at least one cathode active    material, and-   (C) at least one anode comprising at least one anode active    material.

Preferably the electrochemical cell is a secondary lithium ionelectrochemical cell, i.e. secondary lithium ion electrochemical cellcomprising a cathode comprising a cathode active material that canreversibly occlude and release lithium ions and an anode comprising aanode active material that can reversibly occlude and release lithiumions. The terms “secondary lithium ion electrochemical cell” and“(secondary) lithium ion battery” are used interchangeably within thepresent invention.

The at least one cathode active material preferably comprises a materialcapable of occluding and releasing lithium ions selected from lithiatedtransition metal phosphates and lithium ion intercalating transitionmetal oxides.

Examples of lithiated transition metal phosphates are LiFeO₄ andLiCoPO₄, examples of lithium ion intercalating transition metal oxidesare transition metal oxides with layer structure having the generalformula (X) Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0to 0.3; a, b and c may be same or different and are independently 0 to0.8 wherein a+b+c=1; and −0.1≦e≦0.1, and manganese-containing spinels ofgeneral formula (XI) Li_(1+t)M_(2−t)O_(4−d) wherein d is 0 to 0.4, t is0 to 0.4 and M is Mn and at least one further metal selected from thegroup consisting of Co and Ni, andLi_((1+g))[Ni_(h)Co_(i)Al_(j)]_((1−g))O_(2+k). Typical values for g, h,l, j and k are: g=0, h=0.8 to 0.85, i=0.15 to 0.20, j=0.02 to 0.03 andk=0.

In one preferred embodiment the cathode active material is selected fromLiCoPO₄. The cathode containing LiCoPO₄ as cathode active material mayalso be referred to as LiCoPO₄ cathode. The LiCoPO₄ may be doped withFe, Mn, Ni, V, Mg, Al, Zr, Nb, Tl, Ti, K, Na, Ca, Si, Sn, Ge, Ga, B, As,Cr, Sr, or rare earth elements, i.e., a lanthanide, scandium andyttrium. LiCoPO₄ with olivine structure is particularly suited accordingthe present invention due to its high operating voltage (red-oxpotential of 4.8 V vs. Li/Li⁺), flat voltage profile and a hightheoretical capacity of about 170 mAh/g. The cathode may comprise aLiCoPO₄/C composite material. The preparation of a suited cathodecomprising a LiCoPO₄/C composite material is described in Scharabi etal., 2011 and Markevich et al., 2012.

In another preferred embodiment of the present invention the cathodeactive material is selected from transition metal oxides with layerstructure having the general formula (X)Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0 to 0.3; a,b and c may be same or different and are independently 0 to 0.8 whereina+b+c=1; and −0.1≦e≦0.1. Preferred are transition metal oxides withlayer structure having the general formula (X)Li_((1+z))[Ni_(a)Co_(b)Mn_(c)]_((1−z))O_(2+e) wherein z is 0.05 to 0.3,a=0.2 to 0.5, b=0 to 0.3 and c=0.4 to 0.8 wherein a+b+c=1; and−0.1≦e≦0.1. In one embodiment of the present invention, the transitionmetal oxides with layer structure of general formula (X) are selectedfrom those in which [Ni_(a)Co_(b)Mn_(c)] is selected fromNi_(0.33)Co₀Mn_(0.66), Ni_(0.25)Co₀Mn_(0.75), Ni_(0.35)C_(0.15)Mn_(0.5),Ni_(0.21)C_(0.08)Mn_(0.71) and Ni_(0.22)Co_(0.12)Mn_(0.66), inparticular preferred are Ni_(0.21)Co_(0.08)Mn_(0.71) andNi_(0.22)Co_(0.12)Mn_(0.66). The transition metal oxides of generalformula (X) are also called High Energy NCM (HE-NCM) since they havehigher energy densities than usual NCMs. Both HE-NCM and NCM haveoperating voltage of about 3.3 to 3.8 V against Li/Li⁺, but high cut offvoltages (>4.6 V) have to be used for charging HE-NCMS to actuallyaccomplish full charging and to benefit from their higher energydensity.

According to a further preferred embodiment of the present invention thecathode active material is selected from manganese-containing spinels ofgeneral formula (XI) Li_(1+t)M_(2−t)O_(4−d) wherein d is 0 to 0.4, t is0 to 0.4 and M is Mn and at least one further metal selected from thegroup consisting of Co and Ni. An example of a suitedmanganese-containing spinel of general formula (XI) isLiNi_(0.5)Mn_(1.5)O_(4−d). These spinels are also called HV (highvoltage)-spinels.

Many elements are ubiquitous. For example, sodium, potassium andchloride are detectable in certain very small proportions in virtuallyall inorganic materials. In the context of the present invention,proportions of less than 0.5% by weight of cations or anions aredisregarded, i.e. amounts of cations or anions below 0.5% by weight areregarded as non-significant. Any lithium ion-containing transition metaloxide comprising less than 0.5% by weight of sodium is thus consideredto be sodium-free in the context of the present invention.Correspondingly, any lithium ion-containing mixed transition metal oxidecomprising less than 0.5% by weight of sulfate ions is considered to besulfate-free in the context of the present invention.

The cathode may further comprise electrically conductive materials likeelectrically conductive carbon and usual components like binders.Compounds suited as electrically conductive materials and binders areknown to the person skilled in the art. For example, the cathode maycomprise carbon in a conductive polymorph, for example selected fromgraphite, carbon black, carbon nanotubes, carbon nanofibers, graphene ormixtures of at least two of the aforementioned substances. In addition,the cathode may comprise one or more binders, for example one or moreorganic polymers like polyethylene, polyacrylonitrile, polybutadiene,polypropylene, polystyrene, polyacrylates, polyvinyl alcohol,polyisoprene and copolymers of at least two comonomers selected fromethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene,especially styrene-butadiene copolymers, and halogenated (co)polymerslike polyvinlyidene chloride, polyvinly chloride, polyvinyl fluoride,polyvinylidene fluoride (PVdF), polytetrafluoroethylene, copolymers oftetrafluoroethylene and hexafluoropropylene, copolymers oftetrafluoroethylene and vinylidene fluoride and polyacrylnitrile.

Furthermore, the cathode may comprise a current collector which may be ametal wire, a metal grid, a metal web, a metal sheet, a metal foil or ametal plate. A suited metal foil is aluminum foil.

According to one embodiment of the present invention the cathode has athickness of from 25 to 200 μm, preferably of from 30 to 100 μm, basedon the whole thickness of the cathode without the thickness of thecurrent collector.

The anode (C) comprised within the lithium ion secondary battery of thepresent invention comprises an anode active material that can reversiblyocclude and release lithium ions. In particular carbonaceous materialthat can reversibly occlude and release lithium ions can be used asanode active material. Carbonaceous materials suited are crystallinecarbon such as a graphite material, more particularly, natural graphite,graphitized cokes, graphitized MCMB, and graphitized MPCF; amorphouscarbon such as coke, mesocarbon microbeads (MCMB) fired below 1500° C.,and mesophase pitch-based carbon fiber (MPCF); hard carbon and carbonicanode active material (thermally decomposed carbon, coke, graphite) suchas a carbon composite, combusted organic polymer, and carbon fiber.

Further anode active materials are lithium metal, or materialscontaining an element capable of forming an alloy with lithium.Non-limiting examples of materials containing an element capable offorming an alloy with lithium include a metal, a semimetal, or an alloythereof. It should be understood that the term “alloy” as used hereinrefers to both alloys of two or more metals as well as alloys of one ormore metals together with one or more semimetals. If an alloy hasmetallic properties as a whole, the alloy may contain a nonmetalelement. In the texture of the alloy, a solid solution, a eutectic(eutectic mixture), an intermetallic compound or two or more thereofcoexist. Examples of such metal or semimetal elements include, withoutbeing limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium(In), zinc (Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium(Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr) yttrium(Y), and silicon (Si). Metal and semimetal elements of Group 4 or 14 inthe long-form periodic table of the elements are preferable, andespecially preferable are titanium, silicon and tin, in particularsilicon. Examples of tin alloys include ones having, as a secondconstituent element other than tin, one or more elements selected fromthe group consisting of silicon, magnesium (Mg), nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium,bismuth, antimony and chromium (Cr). Examples of silicon alloys includeones having, as a second constituent element other than silicon, one ormore elements selected from the group consisting of tin, magnesium,nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium,germanium, bismuth, antimony and chromium.

A further possible anode active material is silicon which is able totake up lithium ions. The silicon may be used in different forms, e.g.in the form of nanowires, nanotubes, nanoparticles, films, nanoporoussilicon or silicon nanotubes. The silicon may be deposited on a currentcollector. The current collector may be a metal wire, a metal grid, ametal web, a metal sheet, a metal foil or a metal plate. Preferred thecurrent collector is a metal foil, e.g. a copper foil. Thin films ofsilicon may be deposited on metal foils by any technique known to theperson skilled in the art, e.g. by sputtering techniques. Onepossibility of preparing Si thin film electrodes are described in R.Elazari et al.; Electrochem. Comm. 2012, 14, 21-24. It is also possibleto use a silicon/carbon composite as anode active material according tothe present invention.

Another possible anode active material are lithium ion intercalatingoxides of Ti.

Preferably the anode active material present in the inventive lithiumion secondary battery is selected from carbonaceous material that canreversibly occlude and release lithium ions, particularly preferred thecarbonaceous material that can reversibly occlude and release lithiumions is selected from crystalline carbon, hard carbon and amorphouscarbon, in particular preferred is graphite. In another preferredembodiment the anode active material present in the inventive lithiumion secondary battery is selected from silicon that can reversiblyocclude and release lithium ions, preferably the anode comprises a thinfilm of silicon or a silicon/carbon composite. In a further preferredembodiment the anode active material present in the inventive lithiumion secondary battery is selected from lithium ion intercalating oxidesof Ti.

The anode and cathode may be made by preparing an electrode slurrycomposition by dispersing the electrode active material, a binder,optionally a conductive material and a thickener, if desired, in asolvent and coating the slurry composition onto a current collector. Thecurrent collector may be a metal wire, a metal grid, a metal web, ametal sheet, a metal foil or a metal plate. Preferred the currentcollector is a metal foil, e.g. a copper foil or aluminum foil. Theinventive lithium ion batteries may contain further constituentscustomary per se, for example separators, housings, cable connectionsetc. The housing may be of any shape, for example cuboidal or in theshape of a cylinder, the shape of a prism or the housing used is ametal-plastic composite film processed as a pouch. Suited separators arefor example glass fiber separators and polymer-based separators likepolyolefin separators.

Several inventive lithium ion batteries may be combined with oneanother, for example in series connection or in parallel connection.Series connection is preferred. The present invention further providesfor the use of inventive lithium ion batteries as described above indevices, especially in mobile devices. Examples of mobile devices arevehicles, for example automobiles, bicycles, aircraft, or water vehiclessuch as boats or ships. Other examples of mobile devices are those whichare portable, for example computers, especially laptops, telephones orelectrical power tools, for example from the construction sector,especially drills, battery-driven screwdrivers or battery-drivenstaplers. But the inventive lithium ion batteries can also be used forstationary energy stores.

The invention is illustrated by the examples which follow, which do not,however, restrict the invention.

-   1. Origin of Compounds

Compound 8: Diaminomaleonitrile

Purchased from Aldrich.

Compound (1.1): 1,4,5,6-Tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile

Purchased from TCI Europe.

Compounds 8 and (1.1) are shown in Table 1.

TABLE 1 Compound Name Structure 8 Diaminomaleonitrile

(I.1) 1,4,5,6-Tetrahydro-5,6-dioxo-2,3- pyrazinedicarbonitrile

-   2. Electrochemical Cells

Pouch type cells were used to prepare the electrochemical cells. A highvoltage spinel (LiNi_(0.5)Mn_(1.5)O₄, BASF SE) was used as cathodeactive material. A slurry composed of carbon black, graphite, binder andHV-spinel in N-ethyl-2-pyrrolidon (NEP) was prepared in a centrifuge.The slurry was spread onto an aluminum foil and the foil was then driedand cut to dimensions. The electrodes were inserted in a glove box underArgon atmosphere and dried at 120° C. in a vacuum oven. The anode was agraphite anode (Enertek, South Korea, Germany), and a glass fiberseparator was used (Whatman GF/A).

The basic electrolyte composition (LP57) contained a mixture of ethylenecarbonate and ethylmethyl carbonate (3:7 by weight) as solvent and 12.7wt.-% of lithium hexafluorophosphate as conducting salt. The respectiveadditive was solved in the basic electrolyte composition. The amount ofelectrolyte composition used per cell was 105 μl.

The electrochemical testing was done in a Maccor potentiostat Serie 4000at 25° C. Cycling measurements were carried out up to an upper voltageof 4.8 V and to a lower voltage of 3.3 V. The first cycle was done at arate of C/10. A current of 1 C was defined as 148 mA/g. A cycle iscomprised of one charge and one discharge step. The charge was carriedout in constant current—constant voltage mode (CCCV). In this mode, aconstant current is passed through the electrochemical cell until a cellvoltage of 4.8 V was reached. The voltage is then held constant at 4.8 Vuntil the residual current falls to one tenth of its original value orif 30 min have elapsed. The discharge is performed in constant currentmode. A constant current was applied to the electrochemical cell until acell potential of 3.3 V was reached. The cycling program used is shownin Table 2. The steps listed under “Cycling” were repeated severaltimes, i.e. after finishing the 50 cycles at 1 C, the cycling programwas repeated starting with 3 cycles at 1 C, followed by 3 cycles at 2 Cetc. The results of the cycling experiments are shown in Table 3.

TABLE 2 Cycling program Formation Cycling 0.1 C 0.5 C 1 C 2 C 4 C 10 C 1C (14.8 (74 (148 (296 (592 (1480 (148 Rest mA/g) mA/g) mA/g) mA/g) mA/g)mA/g) mA/g) time 2 h Number 2 10 3 3 3 3 50 of cycles Performed oncePerformed multiple times

TABLE 3 Discharge capacity at 1 C C discharge capacity [%] Cycle # 13 50100 300 Comparative LP57 100.0 87.2 75.2 20.5 example 1 ComparativeLP57 + 0.1 wt.- 97.4 88.9 77.8 22.2 example 2 % AcrylonitrileComparative LP57 + 0.5 wt.- 105 97.4 83 22.7 example 3 % AcrylonitrileComparative LP57 + 2 wt.-% 90 72.7 50 5.5 example 4 AcrylonitrileComparative LP57 + 0.5 wt.- 98.7 91.3 82.9 64.4 example 5 % cpd 8Inventive LP57 + 0.5 wt.- 100.0 94.9 88.9 75.2 example 3 % cpd (I.1)

The discharge capacity of the 13^(th) cycle of the comparative example 1(LP 57, the basis electrolyte solution without any additive) was takenas basis value for all discharge capacities displayed in Table 3. It canbe seen that a small amount of acrylonitrile has a beneficial effect onthe discharge capacity, but that this effect is very small after 300cycles. The addition of1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile (compound 1.1)according to the invention results in a pronounced increase of thedischarge capacity even after 300 cycles in comparison to theelectrolyte composition containing the same amount of acrylonitrile.

The invention claimed is:
 1. An electrolyte composition (A) comprising:(i) an aprotic organic solvent comprising a cyclic organic carbonate ora noncyclic organic carbonate; (ii) at least one conducting salt; (iii)at least one compound of formula (I)

wherein X¹ and X² are independently from each other selected from thegroup consisting of N(R¹), P(R¹), O, and S; R¹ is selected from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and C(O)OR³, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)R^(3a), C(O)OR^(3a),NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b); Y¹ and Y² are independently fromeach other selected from the group consisting of (O),(S), (PR²) and(NR²), R² is selected from the group consisting of H, C₁-C₁₀ alkyl,C₃-C₆ (hetero)cycloalkyl, C₂-C₁₀ alkenyl, (hetero)C₃-C₆ cycloalkenyl,C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) andC(O)R^(2a), wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(2b), OS(O)₂R^(2b), S(O)₂R^(2b),OR^(2b), C(O)R^(2b), C(O)OR^(2b), NR^(2b)R^(2c), and NC(O)R^(2b)R^(2c);and R^(2a), R^(2b) and R^(2c) are independently from each other selectedfrom the group consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,C₂-C₁₀ alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl,(hetero)cycloalkyl, alkenyl, and (hetero)aryl may be substituted by oneor more substituents selected from the group consisting of F and CN, R³,R⁴, R^(3a), and R^(3b) are selected independently from each other fromthe group consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl,C₂-C₁₀ alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇(hetero)aryl, and C₇-C₁₃ aralkyl, wherein alkyl, (hetero)cycloalkyl,alkenyl, (hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c),OR^(3c), C(O)R^(3c), C(O) OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);R^(3c) and R^(3d) are selected independently from each other from thegroup consisting of H, C₁-C₁₀ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,alkenyl, and (hetero)aryl may be substituted by one or more substituentsselected from the group consisting of F and CN; and (iv) optionally, atleast one further additive.
 2. The electrolyte composition (A) accordingto claim 1 wherein both Y¹ and Y² are the same and each selected fromthe group consisting of (O) and NR¹.
 3. The electrolyte composition (A)according to claim 1, wherein the at least one compound of formula (I)is compound (I.1)


4. The electrolyte composition (A) according to claim 1, wherein the atleast one compound of formula (I) is selected from a compound of formula(I), wherein X¹ and X² are independently from each other selected fromN(R¹) and O.
 5. The electrolyte composition (A) according to claim 1,wherein the aprotic organic solvent (i) is selected from the groupconsisting of (a) cyclic and noncyclic organic carbonates, which may bepartly halogenated, (b) di-C₁-C₁₀-alkylethers, which may be partlyhalogenated, (c) di-C₁-C₄-alkyl-C₂-C₆-alkylene ethers and polyethers,which may be partly halogenated, (d) cyclic ethers, which may be partlyhalogenated, (e) cyclic and acyclic acetals and ketals, which may bepartly halogenated, (f) orthocarboxylic acids esters, which may bepartly halogenated, (g) cyclic and noncyclic esters of carboxylic acids,which may be partly halogenated, (h) cyclic and noncyclic sulfones,which may be partly halogenated, (i) cyclic and noncyclic nitriles anddinitriles, which may be partly halogenated, and (j) ionic liquids,which may be partly halogenated.
 6. The electrolyte composition (A)according to claim 1, wherein the electrolyte composition (A) containsat least one aprotic solvent (i) selected from cyclic organic carbonatesand at least one aprotic organic solvent (i) selected from noncyclicorganic carbonates.
 7. The electrolyte composition (A) according toclaim 1, wherein the conducting salt (ii) is selected from the groupconsisting of Li[F_(6−x)P(C_(y)F_(2y+1))_(x)], wherein x is an integerin the range from 0 to 6 and y is an integer in the range from 1 to 20;Li[B(R^(I))₄], Li[B(R^(I))₂(OR^(II)O )] and Li[B(OR^(II)O )₂] whereineach R^(I) is independently from each other selected from the groupconsisting of F, Cl, Br, I, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄alkynyl, wherein alkyl, alkenyl, and alkynyl may be substituted by oneor more OR^(III), wherein R^(III) is selected from the group consistingof C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₂-C₆ alkynyl, and (OR^(II)O ) is abivalent group derived from a 1,2- or 1,3-diol, a 1,2- or1,3-dicarboxlic acid or a 1,2- or 1,3-hydroxycarboxylic acid, whereinthe bivalent group forms a 5- or 6-membered cycle via the both oxygenatoms with the central B-atom; LiClO₄; LiAsF₆; LiCF₃SO₃; Li₂SiF₆;LiSbF₆; LiAlCl₄, lithium tetrafluoro (oxalato) phosphate; lithiumoxalate; and salts of the general formula Li[Z(C_(n)F_(2n+1)SO₂)_(m),],where m and n are defined as follows: m=1 when Z is selected from thegroup consisting of oxygen and sulfur, m=2 when Z is selected from thegroup consisting of nitrogen and phosphorus, m=3 when Z is selected fromthe group consisting of carbon and silicon, and n is an integer in therange from 1 to
 20. 8. The electrolyte composition (A) according toclaim 1, wherein the electrolyte composition (A) contains at least onefurther additive (iv) which is selected from the group consisting ofvinylene carbonate and its derivatives, vinyl ethylene carbonate and itsderivatives, methyl ethylene carbonate and its derivatives, lithium(bisoxalato) borate, lithium difluoro (oxalato) borate, lithiumtetrafluoro (oxalato) phosphate, lithium oxalate, 2-vinyl pyridine,4-vinyl pyridine, cyclic exo-methylene carbonates, sultones, organicesters of inorganic acids, acyclic and cyclic alkanes having a boilingpoint at 1 bar of at least 36° C., and aromatic compounds, optionallyhalogenated cyclic and acyclic sulfonylimides, optionally halogenatedcyclic and acyclic phosphate esters, optionally halogenated cyclic andacyclic phosphines, optionally halogenated cyclic and acyclicphosphites, optionally halogenated cyclic and acyclic phosphazenes,optionally halogenated cyclic and acyclic silylamines, optionallyhalogenated cyclic and acyclic halogenated esters, optionallyhalogenated cyclic and acyclic amides, optionally halogenated cyclic andacyclic anhydrides, ionic liquids, and optionally halogenated organicheterocycles.
 9. The electrolyte composition (A) according to claim 1,wherein the concentration of the at least one compound of formula (I) is0.001 to 10 wt.-%, based on the total weight of the electrolytecomposition (A).
 10. The electrolyte composition (A) according to claim1, wherein the concentration of the at least one compound of formula (I)0.01 to 2 wt.-%, based on the total weight of the electrolytecomposition (A).
 11. An electrochemical cell comprising: (A) theelectrolyte composition according to claim 1, (B) at least one cathodecomprising at least one cathode active material, and (C) at least oneanode comprising at least one anode active material.
 12. Theelectrochemical cell according to claim 11 wherein the electrochemicalcell is a secondary lithium ion battery.
 13. The electrochemical cellaccording to claim 11 wherein at least one cathode active materialcomprises a material capable of occluding and releasing lithium ionsselected from the group consisting of lithiated transition metalphosphates and lithium ion intercalating transition metal oxides. 14.The electrochemical cell according to claim 11, wherein the at least oneanode active material comprises a lithium ion intercalating materialselected from the group consisting of lithium ion intercalatingcarbonaceous material, lithium ion intercalating oxides of Ti, andlithium ion uptaking silicon.
 15. A method for producing anelectrochemical cell comprising incorporating into an electrochemicalcell as an electrolyte a compound of formula (I):

wherein X¹and X² are independently from each other selected from thegroup consisting of N(R¹), P(R¹), O, and S; R¹ is selected from thegroup consisting of H, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₃-C₆ (hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl,C₇-C₁₃ aralkyl, OR³, C(O)R³, C(NR³)R⁴, and C(O)OR³, wherein alkyl,(hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl, alkynyl,(hetero)aryl, and aralkyl may be substituted by one or more substituentsselected from the group consisting of F, CN, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3a),OS(O)₂R^(3a), S(O)₂R^(3a), OR^(3a), C(O)OR^(3a), C(O)OR^(3a),NR^(3a)R^(3b), and NC(O)R^(3a)R^(3b); Y¹ and Y² are independently fromeach other selected from the group consisting of (O), (S), (PR²) and(NR²), R² is selected from the group consisting of H, C₁-C₆ alkyl, C₃-C₆(hetero)cycloalkyl, C₂-C₆ alkenyl, (hetero)C₃-C₆ cycloalkenyl, C₂-C₆alkynyl, C₅-C₇ (hetero)aryl, C₇-C₁₃ aralkyl, OR^(2a) and C(O)R^(2a),wherein alkyl, (hetero)cycloalkyl, alkenyl, (hetero)cycloalkenyl,alkynyl, (hetero)aryl, and aralkyl may be substituted by one or moresubstituents selected from the group consisting of F, CN, C₁-C₆ alkyl,C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₅-C₇ (hetero)aryl,S(O)₂OR^(2b), OS(O)₂R^(2b), S(O)₂R^(2b), OR^(2b), C(O)R^(2b),C(O)OR^(10b), NR^(2b)R^(2c), and NC(O)R^(2b) R^(2c); and R^(2a), R^(2b)and R^(2c) are independently from each other selected from the groupconsisting of H, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl,and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl, alkenyl, and(hetero)aryl may be substituted by one or more substituents selectedfrom the group consisting of F and CN, R³, R⁴, R^(3a), and R^(3b) areselected independently from each other from the group consisting of H,C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆ alkenyl, C₃-C₆(hetero)cycloalkenyl, C₂-C₆ alkynyl, C₅-C₇ (hetero)aryl, and C₇-C₁₃aralkyl, wherein alkyl, (hetero)cycloalkyl, alkenyl,(hetero)cycloalkenyl, alkynyl, (hetero)aryl, and aralkyl may besubstituted by one or more substituents selected from the groupconsisting of F, CN, C₁-C₆ alkyl, C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, C₅-C₇ (hetero)aryl, S(O)₂OR^(3c), OS(O)₂R^(3c), S(O)₂R^(3c),OR^(3c), C(O)R^(3c), C(O)OR^(3c), NR^(3c)R^(3d), and NC(O)R^(3c)R^(3d);R^(3c) and R^(3d) are selected independently from each other from thegroup consisting of H, C₁-C₆ alkyl C₃-C₆ (hetero)cycloalkyl, C₂-C₆alkenyl, and C₅-C₇ (hetero)aryl, wherein alkyl, (hetero)cycloalkyl,alkenyl, and (hetero)aryl may be substituted by one or more substituentsselected from the group consisting of F and CN.